BR112019025357B1 - SANITIZING AND/OR ANTIMICROBIAL DISINFECTANT TREATMENT METHOD AND BLEACHING OF WASHING CLOTHES - Google Patents

Abstract

A method for enhancing bleaching effectiveness for laundry care is disclosed. Methods for sanitizing and/or disinfecting and whitening laundry and other articles are provided by washing the articles with a peroxyformic acid composition at a pH of 4 to 7 for effective antimicrobial efficacy, thereafter applying an alkaline source to raise the pH to at least least above 9 for adding a bleach activator and/or catalyst to enhance the bleaching effectiveness of the peroxyformic acid, and finally draining the remaining components of the peroxyformic acid composition and the bleach activator/catalyst from the articles. The methods are provided as part of a laundry cleaning operation and may be used in industrial and commercial applications.

Description

CROSS-REFERENCE TO RELATED ORDERS

[001] This application claims priority from US provisional application Serial No. 62/523,360, filed June 22, 2017, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[002] Methods for enhancing bleaching effectiveness are provided for bleaching articles, namely laundry. In particular, laundry may be treated by washing the laundry with a peroxyformic acid composition at a pH first for effective antimicrobial efficacy, thereafter applying an alkaline source to raise the pH for addition of a bleach activator and/or catalyst for the bleaching agent at a second pH, and finally draining the remaining components of the peroxyformic acid composition and the bleaching agent and bleach activator/catalyst from the laundry. Beneficially, this method of whitening laundry can be provided as part of a laundry cleaning operation and can be used in industrial and commercial applications. Even more beneficially, this method of whitening laundry can be used as a part of a laundry cleaning application that provides antimicrobial efficacy against various difficult-to-treat organisms and at various temperatures.

BACKGROUND OF THE INVENTION

[003] In industrial and commercial laundry facilities, textile materials such as sheets, towels, handkerchiefs, clothes, tablecloths, etc. are often washed at elevated temperatures at alkaline pH. The alkalinity can be provided through a single alkaline detergent or, alternatively, the alkalinity can be provided from one product, while the other detergent components, including surfactants, chelants, water conditioners and/or other detergent materials, are provided in a second. product. In other markets, textile materials are often washed with neutral detergents with a separate alkaline product combined in one wash. Detergents can be combined in a laundry application with various additional components such as bleaches, bleaching agents, anti-redeposition agents, etc., which are used to enhance the appearance of the resulting textile materials. Various additional components can optionally be dosed separately from the alkaline detergent and will either be mixed into the laundry bath or into a separate laundry bath liquor. For example, in some laundry applications, there are discrete dosing and rinsing steps where there is a rinse between a detergent and bleach step. In other laundry applications, such as a tunnel washer, multiple addition steps employ mixing of the components. In each of these end-of-cycle applications, textiles that have been treated with an alkaline detergent are typically treated with a commercial or industrial acidic composition that contains acidic components to neutralize alkaline residues in the fabric to enhance skin compatibility.

[004] In a conventional industrial laundry laundry facility, textile materials may be subjected to multiple treatment steps in an industrial-sized washing machine to provide antimicrobial effectiveness. Exemplary treatment steps include a pre-soaking step, a washing step that often occurs at a pH of about 11 to 12, a rinsing step, and/or multiple rinsing steps for removing soil-containing wash liquor that incrementally lowering the pH and an acidic step that brings the final pH to around 5 to 7 and an extraction step that often involves twirling textiles to remove water. An antimicrobial composition can be applied simultaneously with the detergent, such as an all-in-one product for powders and solids or simultaneous dosing of separate products, immediately following the detergent step or during the acid step where minimal contact time is provided in the absence of other cleaning chemicals. Laundry applications can range from simultaneous dosing of detergent and other cleaning chemicals.

[005] There remains a need to improve laundry techniques for industrial laundry and provide enhanced efficiency, along with other improvements such as a reduction in processing time, cost of materials, material consumption, energy costs and energy consumption. Water. Accordingly, it is an objective of the methods to improve one or more of these aspects of laundry techniques for laundering. It is an additional object to improve the antimicrobial and bleaching effectiveness of laundry through the use of peroxyformic acid compositions.

[006] An object of the methods is to enhance the bleaching effectiveness for bleaching laundry articles employing a peroxyformic acid composition.

[007] Other objects, advantages and features of the present invention will become evident from the following descriptive report taken in conjunction with the attached drawings.

BRIEF SUMMARY OF THE INVENTION

[008] An advantage of the methods of sanitizing and/or disinfecting and whitening laundry is that the methods do not require peroxycarboxylic acid of high actives in ppm to effectively sanitize and/or disinfect and whiten laundry when used in combination with a catalyst and/or activator. A method for treating laundry is provided. More particularly, a method of whitening laundry is provided.

[009] In the present methods, a process for sanitizing and/or disinfecting and whitening laundry is provided, where the peroxyformic acid composition, a detergent composition, alkaline activator and bleach and/or catalyst are dosed. This differs from certain conventional methods in many regions by placing the sanitizing step before the washing step, rather than following it, providing several benefits provided by the use of peroxyformic acid: 1) bleach activators and/or catalysts can now be used with oxygen-based peroxyformic acid composition for improved whitening and antimicrobial activity; and 2) peroxyformic acid compositions require lower actives compared to C2 or greater carbon chain fatty acid antimicrobial composition.

[0010] In one embodiment, a method of antimicrobial treatment and bleaching of laundry includes the steps of (a) washing the laundry with a peroxyformic acid composition in a pH range of about 4 to about 7 in a washing machine for antimicrobial effectiveness in laundry, wherein the peroxyformic acid composition comprises peroxyformic acid, formic acid and hydrogen peroxide; (b) adding an alkalinity source to the washing machine to raise the pH range to at least above 9, preferably at least about 10.5, in the washing machine; (c) applying a detergent use solution to remove soil from the laundry and adding a bleach activator and/or catalyst composition to enhance the bleaching effectiveness of the peroxyformic acid composition to the laundry in the washing machine; and (d) draining the peroxyformic acid composition, the detergent use solution, and the bleach activator and/or catalyst composition from the laundry. In a further embodiment of the methods, the peroxyformic acid composition has a ratio of peroxyformic acid to hydrogen peroxide of at least 1:1 to about 1:1.5 or at least 1:1 to about 1:2 or at least less than 1:1 to about 1:3 or greater and/or the method comprises the further step of adding additional hydrogen peroxide to the washing machine wash to increase the bleaching effectiveness of the peroxyformic acid composition.

[0011] In a further embodiment, the peroxyformic acid composition is applied to laundry for washing in a washing machine at a pH of about 5 to about 7, from about 6 to about 8 or about 7. In an additional embodiment, the peroxyformic acid composition is applied to the laundry for washing in the washing machine for about 3 to about 15 minutes, or for about 5 to about 10 minutes. In a further embodiment, the peroxyformic acid composition is generated in situ or at a point of use. In a further embodiment, the peroxyformic acid composition is fed to the washing machine at an active active level of from about 5 ppm to about 200 ppm, or from about 5 ppm to about 80 ppm.

[0012] In an additional embodiment, the alkalinity source raises the pH range to at least above 10, from about 10 to about 11, or at least about 11. detergent and the bleach activator and/or catalyst composition is applied to the laundry for washing in the washing machine for about 3 to about 15 minutes, or for about 5 to about 10 minutes. In a further embodiment, the method includes a step of rinsing the peroxyformic acid composition, the detergent use solution and the bleach activator and/or catalyst composition from the laundry including wherein the laundry is rinsed with water in the washing machine for at least about 1 minute or from about 1 minute to about 6 minutes. In still other embodiments, the method further comprises an adjunct solution comprising at least one of acidity agents, fabric softening agents, starch, anti-wrinkling agents, sizing agents, color fasting agents, oil and water repellent agents, water conditioning agents, iron control agents, water threshold agents, soil release agents, soil protection agents, optical brightening agents, fragrances and mixtures thereof. Further, the adjunctive use solution is applied to the laundry for washing in the washing machine at a pH of about 5 to about 8 for about 1 to about 6 minutes.

[0013] While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Consequently, the drawings and the detailed description will be considered as illustrative and not restrictive in nature.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG. 1 shows a soil removal graph representing bleaching effectiveness according to methods.

[0015] FIG. 2 shows a pH titration comparing antimicrobial actives according to method modalities.

[0016] FIGS. 3-5 show representations of methods according to modalities of dosing a peroxyformic acid composition for enhanced bleaching in combination with an oxygen catalyst and/or bleach activator.

[0017] Various embodiments of the present invention will be described in detail with reference to the drawings, in which like reference numerals represent like parts throughout the various views. Reference to various embodiments does not limit the scope of the invention. The Figures represented in the present document are not limitations for the various embodiments according to the invention and are presented for exemplary illustration of the invention.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY

[0018] Embodiments of this invention are not limited to particular methods of incorporating a bleaching step into a laundry application, which may vary and are understood by those skilled in the art. It is to be further understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting in any way. For example, when used in this specification and the accompanying claims, the singular forms “a”, “an”, “the” and “the” may include plural referents, unless the content clearly indicates otherwise. Furthermore, all units, prefixes, and symbols can be represented in their SI-accepted form.

[0019] The numerical ranges mentioned in the descriptive report include the numbers within the defined range. Throughout this disclosure, various aspects of this invention are presented in a banner format. It is understood that the description in banner format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Consequently, the description of a range should be considered to have specifically disclosed all possible subranges as well as individual numerical values within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3, 80, 4 and 5).

[0020] In order that the present invention may be more readily understood, certain terms are defined first. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which embodiments of the invention belong. Many methods and materials similar, modified, or equivalent to those described herein can be used in practicing embodiments of the present invention without undue experimentation, with preferred materials and methods described herein. In describing and claiming embodiments of the present invention, the following terminology will be used in accordance with the definitions set forth below.

[0021] The term “about”, as used in this document, refers to the variation in numerical quantity that may occur, for example, through typical measurement and handling procedures for liquids used to produce concentrates or solutions for use in the world real; through inadvertent errors in these procedures; through differences in the manufacture, source or purity of the ingredients used to produce the compositions or carry out the methods; and the like. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular starting mixture. Whether or not modified by the term "about", the claims include equivalent amounts.

[0022] The terms “actives” or “percentage of actives” or “percentage by weight of actives” or “concentration of actives” are used interchangeably herein and refer to the concentration of those ingredients involved in cleaning expressed as a percentage minus ingredients inert materials such as water or salts.

[0023] An "anti-redeposition agent" refers to a compound that helps to stay suspended in water, rather than redeposit on the object being cleaned. Anti-redeposition agents are useful in the present methods to help reduce redeposition of removed soil on the surface being cleaned.

[0024] As used herein, the term “cleaning” refers to a method used to facilitate or assist in the removal of dirt, bleaching, microbial population reduction, rinsing, and any combination thereof. As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonial) organisms. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virines, viroids, viruses, phages, and some algae. As used herein, the term "microbe" is synonymous with microorganism.

[0025] As used herein, the term "disinfectant" refers to an agent that eliminates all vegetative cells including most recognized pathogenic microorganisms, using the procedure described in A.O.A.C. Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2).

[0026] The terms “include” and “including” when used in reference to a list of materials refer to, but are not limited to, the materials so listed.

[0027] The term “laundry” refers to items or articles that are cleaned and/or microbial population reduced in a washing machine. In general, laundry refers to any item or article made from or including textile materials, woven fabrics, non-woven fabrics and knitted fabrics. Textile materials can include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers and blends thereof, which include blends of cotton and polyester. The fibers can be treated or untreated. Exemplary treated fibers include those treated for flame retardancy. It should be understood that the term "white linen" is often used to describe certain types of laundry items including bed sheets, pillowcases, towels, tablecloths, tablecloths, bar scrubs and uniforms. It should be understood that the term "white linen" is often used to describe certain types of laundry items, including bed sheets, pillowcases, towels, tablecloths, tablecloths, bar scrubs and uniforms.

[0028] As used herein, the term "peroxy acid" may also be referred to as "peroxycarboxylic acid", "percarboxylic acid" or "peroxy acid". Sulfoperoxycarboxylic acids, sulfonated peroxy acids and sulfonated peroxycarboxylic acids are also included within the term "peracid" as used herein. The terms "sulfoperoxycarboxylic acid", "sulfonated peroxyacid" or "sulfonated peroxycarboxylic acid" refer to the peroxycarboxylic acid form of a sulfonated carboxylic acid, as disclosed in US Patent Publications 2010/0021557, 2010/0048730 and 2012/0052134, which are incorporated herein by reference in their entirety. A peracid refers to an acid that has the hydrogen of the hydroxyl group in the carboxylic acid replaced by a hydroxyl group. Oxidizing peracids may also be referred to herein as peroxycarboxylic acids.

[0029] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as, for example, block, graft, random and alternating copolymers, terpolymers and "x"mers higher levels, additionally including their derivatives, their combinations and mixtures thereof. Additionally, unless specifically limited otherwise, the term "polymer" shall include all possible isomeric configurations of the molecule, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Additionally, unless specifically limited otherwise, the term "polymer" shall include all possible geometric configurations of the molecule.

[0030] The term “soft surface” refers to a resilient washable substrate, for example, materials made from woven, non-woven or knitted textiles, leather, rubber or flexible plastics including fabrics (for example, surgical gowns, drapes, bedding, dressings, etc.), carpeting, transport vehicle seats and interior components and the like. As noted here, laundry and white linen are included on soft surfaces.

[0031] As used herein, the term "dirt" refers to polar or non-polar organic or inorganic substances including, but not limited to, carbohydrates, proteins, fats, oils and the like. These substances may be present in their organic state or complexed with a metal to form an inorganic complex.

[0032] As used herein, the term "stain" refers to a polar or non-polar substance that may or may not contain particulate matter, such as metal oxides, metal hydroxides, metal oxides-hydroxides, clays, sand, dust, natural matter, carbon black, graphite and similar

[0033] As used in this disclosure, the term "sporicide" refers to a physical or chemical agent or process having the ability to cause more than 90% reduction (1 log order reduction) in the spore population of Bacillus cereus or Bacillus subtilis within a defined time and temperature established by the relevant regulatory authority. In certain embodiments, the sporicidal compositions of the invention provide greater than 99% reduction (2 log order reduction), greater than 99.99% reduction (4 log order reduction), or greater than 99.999% reduction (4 log reduction). order 5 log) in such a population.

[0034] The differentiation of “acid" or “static” antimicrobial activity, whose definitions describe the degree of effectiveness and the official laboratory protocols for measuring this effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is an irreversible lethal action that results in the complete destruction or incapacitation of the microbial cell. The second type of cell damage is reversible, so that if the organism is free of the agent, it can multiply again. The first is termed microbiocidal and the second microbiostatic. A sanitizer and a disinfectant are, by definition, agents that provide antimicrobial or microbiocidal activity. Efficacy according to the methods is effective against a wide range of bacteria, including gram- positive and gram-negative. Exemplary bacteria include, for example, Escherichia spp., Staphylococcus spp., Kl ebsiella spp., Enterococcus spp., Acinetobacter spp., Pseudomonas spp., Streptococcus spp., including for example Escherichia Coli, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), Staphylococcus epidermidis, Klebsiella Pneumonia including Carbapenem Resistant Klebsielle Pneumonia, Enterococcus faecalis, Enterococcus hirae, Acinetobacter baumannii, Pseudomonas aeruginosa, Streptococcus pyogenes, Mycobacterium terrae and Mycobacterium avium. In addition to bacteria, it is understood that viruses, fungi, Mycobacteria, yeast and spores can also be treated by the methods disclosed herein.

[0035] As used herein, the term "substantially free" refers to compositions lacking the component completely or having such a small amount of the component that the component does not affect the performance of the composition. The component can be present as an impurity or as a contaminant and must be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0036] The term “threshold agent” refers to a compound that inhibits the crystallization of water hardness ions from solution, but which need not form a specific complex with the water hardness ion. Threshold agents include, but are not limited to, a polyacrylate, a polymethacrylate, an olefinic/maleic copolymer, and the like.

[0037] The term "water-soluble" refers to a compound that can be dissolved in water at a concentration greater than 1% by weight. The terms "sparsely soluble" or "sparsely soluble in water" refer to a compound that can be dissolved in water only to a concentration of 0.1 to 1.0% by weight. The term "water insoluble" refers to a compound that can be dissolved in water only to a concentration of less than 0.1% by weight.

[0038] The term "percentage by weight", "% by weight" and variations thereof, as used herein, refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used herein, "percent", "%" and the like are intended to be synonymous with "percent by weight", "% by weight", etc.

[0039] The methods, systems and compositions of the present invention may comprise, consist essentially of, or consist of components and ingredients of the present invention, as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods, systems and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and innovative characteristics of the methods, systems and compositions claimed.

[0040] It should also be noted that, as used in this specification and the accompanying claims, the term "configured" describes a system, apparatus or other structure that is built or configured to perform a particular task or adopt a particular configuration. The term "configured" can be used interchangeably with other similar phrases, such as arranged and configured, constructed and disposed, adapted and configured, adapted, constructed, manufactured and disposed, and the like. Antimicrobial Treatment Methods (Sanitization and/or Disinfection) and Bleaching of Laundry Clothes

Clothes Washing Machines

[0041] A method for treating laundry is provided. A washing machine is provided. The washing machine includes a drum having an interior for holding laundry, a motor constructed and arranged to rotate the drum, a water inlet for introducing water into the interior of the drum, a chemical inlet for introducing chemicals into the drum , a drain to allow fluid to drain from the inside of the drum, and a processing unit built to operate the washing machine. The processing unit can be constructed to provide a wash to wash cycle, an antimicrobial, disinfectant and bleach cycle (which can be pre-wash or post-wash cycle) and a detergent use solution with an activator cycle bleaching agent and/or catalyst to remove dirt from laundry and enhance peroxyformic acid bleaching according to methods.

[0042] The method for treating laundry can be provided in a commercial and/or industrial laundry washing facility and can be provided in a residential and/or domestic washing machine that is programmable. Examples of commercial and/or industrial laundry facilities include those cleaning textiles for the rental, healthcare and hospitality industries. Furthermore, the method of treating laundry may occur as part of an operation that includes additional steps such as washing, rinsing, finishing and extracting. Furthermore, it should be understood that the step of treating laundry for laundry may include, as part of the step, additional activities, such as, for example, washing and finishing.

[0043] Many commercial and industrial washing machines are able to manipulate the method to treat laundry according to the methods. Many commercial and industrial washing machines are computer programmable and computer programs can be provided to operate the machines according to the methods. Furthermore, it is expected that machines can be made available to treat laundry according to the methods and that these machines can be used in both industrial and commercial applications and in domestic and residential applications. Furthermore, the treatment composition can be formulated so that it can be used in commercial and industrial washing machines and in residential washing machines that are in common use and are computer programmable without modification.

[0044] In some embodiments, the methods are suitable for use in washer-extractor machines. In one embodiment, the methods can be applied to a front loading horizontal axis washer. In another embodiment, the methods can be applied to a top loading washer. The washing machines that can be used according to the methods can be characterized as horizontal axis or vertical axis washing machines, depending on the axis of rotation.

[0045] In other embodiments, tunnel washers and continuous bath washers can be used according to the methods. A tunnel washer consists of several compartments that are arranged in a tunnel-like construction. The laundry remains in each compartment for a certain amount of time and is then transported to the next compartment by top or bottom transfer. Each compartment can be connected to a dosing unit that allows the addition of one or more laundry components. In this way, the first component cleaning and disinfecting composition and the second component bleaching and disinfecting composition, as well as other laundry treatment chemicals, can be independently added to various compartments of the tunnel washer.

Washing Clothes / Textiles

[0046] Any of a variety of textile articles can benefit from being washed according to the present method. Suitable textiles include those for hospitality, healthcare, industrial and food service facilities. In one embodiment, the textile cleaned by the present is a white textile article or a colored synthetic textile article (e.g., polyester). In one embodiment, the textile is a white cotton textile article. In one embodiment, the textiles are from a health care institution. That is, textiles are textile articles used in health care. Such healthcare textile articles include, for example, a sheet, towel, patient gown, bed blanket, incontinence pad, operating room linen, mop, wash cloth, pillowcase or a mixture thereof.

Methods

[0047] A general representation of the methods is shown in FIGS. 34. In one embodiment, the methods include at least providing a peroxyformic acid composition for disinfecting and/or bleaching; thereafter, increase the pH of the wash with an alkaline source to raise the pH to the range where the oxygen catalyst is effective; providing a catalyst to activate available oxygen in the peroxyformic acid composition to improve low temperature bleaching; and, optionally, adding additional bleaching composition. As used herein, the phrase "low temperature" refers to a temperature of about 50°C maximum.

[0048] Laundry care methods can provide antimicrobial and bleaching treatment and employ a peroxyformic acid composition. The peroxyformic acid composition comprises peroxyformic acid, formic acid and hydrogen peroxide. Additional components can be included in the peroxyformic acid composition. The peroxyformic acid composition can be provided in the form of a concentrate which is diluted with water to provide a use solution. The use solution can be used to wash items such as laundry.

[0049] The method for treating laundry may be provided as part of a general method for cleaning laundry. That is, as part of a laundry cleaning operation, the laundry may be treated with an antimicrobial and bleaching composition to provide antimicrobial and bleaching properties. Antimicrobial properties can be characterized as sanitizing when there is a substantial reduction of bacteria, fungi, spores and other microorganisms or microorganism-generating materials on a surface being treated to provide a sanitized surface. A substantial reduction refers to a reduction of at least three orders of magnitude and may be referred to as a three log10 reduction. Preferably, the reduction can be at least four orders of magnitude and more preferably at least five orders of magnitude.

[0050] The method for treating laundry relates to treating laundry with the peroxyformic acid composition as substantially shown and represented in FIGS. 3-5. The methods include the step of washing the laundry with a peroxyformic acid composition at a pH range of about 4 to about 7 for antimicrobial effectiveness, followed by adding an alkalinity source to the washing machine to increase the pH up to an alkaline range for detergent composition containing a bleach activator (FIG. 3), catalyst (FIG. 4) or combination (FIG. 5) for bleaching effectiveness and subsequently drain PFA, bleach catalyst and/or activator . As noted herein, the detergent composition can include surfactants, cleaning agents and other components conventionally formulated in detergents; however, in a further embodiment, the detergent composition may consist or consist essentially of the bleach activator and/or bleach catalyst. In some embodiments where the detergent composition is neutral or low alkaline detergent, an additional step of adding alkalinity prior to or concurrent with dosing the detergent composition can be included in the methods. In yet a further embodiment, the PFA and the detergent and/or alkalinity source can be dosed simultaneously, such various modalities are included within the scope of the methods described and represented in this document.

[0051] In some embodiments, the wash step employing a peroxyformic acid composition may be preceded by an initial wash step (shown as optional in FIGS. 3-5). In some embodiments, the initial wash step is not a highly alkaline step; it can include a neutral step or a low alkaline step, and in these embodiments, the peroxyformic acid is capable of lowering the pH on its own. However, in some embodiments, an initial wash step that is more alkaline is not preferred, as the method would require the step of lowering the pH to the desired range (such as between about 4 and about 8) for antimicrobial effectiveness. of peroxyformic acid followed by an initial wash step (such as an alkaline detergent composition).

[0052] The methods may further include the step of adding additional hydrogen peroxide (or active oxygen) to the wash (FIG. 5) to further enhance the bleaching effectiveness of the methods. The addition of additional hydrogen peroxide (or active oxygen) can be added to the system at various points, as shown in FIG. 5, including, for example, before/simultaneously/after the peroxyformic acid composition, before/simultaneously/after the alkalinity source and/or before/simultaneously/after the detergent composition.

[0053] The conditions for employing the peroxyformic acid composition include contacting the laundry to be washed with the peroxyformic acid composition at a pH of from about 2 to about 10, from about 2 to about 9, from about 2 to about 8, from about 4 to about 9, from about 4 to about 8, from about 4 to about 7, from about 5 to about 8, or preferably less than about 7 to provide a pH that favors antimicrobial treatment. In some embodiments, a pH of at least 4 is preferred to ensure that an acidic pH does not damage the laundry fabric and less than about 7 for peroxyformic acid microefficacy. In preferred embodiments, the laundry treatment with the peroxyformic acid composition is at a pH of from about 4 to about 7, or more preferably, from about 5 to about 7, and most preferably, from about 6. to about 7. In one aspect, the method of applying the peroxyformic acid composition to laundry for washing in a washing machine is for a period of time of at least a few minutes, or about 3 to about 15 minutes, or for about 5 to about 10 minutes. In general, it is expected that sufficient antimicrobial effect can occur in a time between about 1 and about 20 minutes, in a time between about 2 and about 15 minutes, and a time between about 3 minutes and about 10 minutes .

[0054] Thereafter, the method for treating laundry includes the step of adding a source of alkalinity to the washing machine to increase the pH range to at least about 7, at least above 8, above 8, above from about 9, above 10, from about 10 to about 11, or at least about 11. Any suitable alkalinity source can be employed in accordance with the methods. Exemplary alkalinity sources include at least one of alkali metal hydroxide, alkali metal silicate, alkali metal carbonate or other base components. As one skilled in the art will appreciate, the increase in pH by the source of alkalinity is pH dependent. A lower temperature range employed in the antimicrobial and/or bleaching step will require a lower pH adjustment.

[0055] Thereafter, the method for treating laundry includes providing a detergent use solution and a bleach activator and/or catalyst at an alkaline pH, at a pH greater than about 7, preferably at a pH from about 9 to about 13 to provide a pH that favors bleaching effectiveness. The detergent use solution and the bleach activator and/or catalyst composition are applied to the laundry for washing in the washing machine for about 3 to about 15 minutes, or for about 5 to about 10 minutes. In general, it is expected that sufficient whitening can occur in a time between about 1 and about 20 minutes, in a time between about 2 and about 15 minutes, and a time between about 3 minutes and about 10 minutes.

[0056] The detergent use solution may be a neutral to highly alkaline detergent use solution. In general, an alkaline wash is expected to refer to a wash that occurs at a pH between about 7 and about 13 and can include a pH between about 8 and about 12. As noted herein, the solutions for use of detergent include an alkalinity agent. Exemplary alkalinity agents include at least one of alkali metal hydroxide, alkali metal silicate, alkali metal carbonate or other base components. The detergent use solution can further include any one or more of surfactants, chelants, polymers, enzymes or other functional ingredients.

[0057] The method for treating laundry may optionally include the additional step of adding hydrogen peroxide to the washing machine wash to increase the bleaching effectiveness of the peroxyformic acid composition. Additional hydrogen peroxide added to the washing machine to increase bleaching effectiveness can be dosed at various points in the method including before/simultaneously/after the peroxyformic acid compounding, before/simultaneously/after the alkali source and/or before/ simultaneously/after detergent composition.

[0058] The method of treating laundry may optionally include the additional step of rinsing the peroxyformic acid composition, the detergent use solution, and the bleach activator and/or catalyst composition from the laundry. In one aspect, the laundry is rinsed with water in the washing machine for at least about 1 minute or from about 1 minute to about 6 minutes. Beneficially, according to the methods the peroxyformic acid composition degrades into its inert components and therefore does not remain in solution in the laundry as much as biocides and/or other conventional sanitizing components. Therefore, the rinse and drain step effectively removes the detergent use solution and the bleach activator and/or catalyst composition from the laundry. As depicted in the figures, the various draining steps can optionally include a rinsing step before or after draining. The method of treating laundry can optionally include the additional step of adding an adjunct solution comprising at least one of acidifying agents, fabric softening agents, starch, anti-wrinkling agents, sizing agents, color fasting agents , oil and water repellent agents, water conditioning agents, iron control agents, water threshold agents, soil release agents, soil protection agents, optical brightening agents, fragrances and mixtures thereof. In one aspect, the addition of the adjunctive use solution can be added at any stage of the process to enhance the cleaning and/or sanitizing and/or disinfecting and bleaching of the laundry. In one aspect, the adjunctive use solution is applied to laundry for washing in a washing machine at a pH of about 5 to about 8 for about 1 to about 6 minutes.

[0059] Although not depicted in the figures, in a preferred embodiment, a finishing or acid step is added after draining the peroxyformic acid and bleach compositions. In such embodiments, any number of draining and/or rinsing steps may precede the finishing or aciding step.

[0060] In a preferred aspect, the method of sanitizing and/or disinfecting and bleaching the laundry laundry precedes an additional washing step to disinfect the laundry laundry and remove bacteria, viruses or other contaminants from the laundry laundry. Beneficially, according to this aspect, disinfection kills bacteria, viruses or other contaminants before any wash water is discharged from the washing machine. However, in other respects, the method of sanitizing and/or disinfecting and bleaching laundry laundry follows an initial laundering step for the laundry laundry.

Peroxyformic Acid Compositions

[0061] The peroxyformic acid compositions provide the antimicrobial and whitening efficacy according to the methods. It is desirable to provide the treatment use composition at a pH that favors antimicrobial and bleaching treatment first at a relatively low pH to effect a desired level of antimicrobial treatment and bleaching at a higher pH (as achieved by dosing the alkalinity source ) in order to affect the desired level of whitening through the use of a bleach activator and/or catalyst that is effective to whiten without damaging laundry (e.g. textile substrates) at alkaline pH. As one skilled in the art understands that using the bleaching component at a more acidic pH can cause damage to the laundry. Furthermore, in order to take advantage of the possible carryover effect of a washing step using an alkaline detergent use solution, it may be advantageous to first supply the peroxyformic acid composition at a relatively low pH and then perform a washing cycle with an alkaline detergent that provides the bleaching operation with a pH that favors bleaching.

[0062] Peroxyformic acid compositions may include equilibrium or non-equilibrium compositions comprising, consisting and/or consisting essentially of peroxyformic acid, formic acid, hydrogen peroxide and water. Additional components can be included in the peroxyformic acid composition. A peroxyformic acid composition can be supplied to a washing machine as a concentrate or a use solution. A peroxyformic acid composition can be generated on-site or off-site and supplied to a washing machine.

[0063] In some embodiments, the peroxyformic acid compositions according to the methods include a higher ratio of hydrogen peroxide as found in conventional peracid compositions. In one aspect, the ratio of peroxyformic acid to hydrogen peroxide is from about 1:1 to about 1:2, about 1:1 to about 1:1.5. In a further aspect, the ratio of peroxyformic acid to hydrogen peroxide can be lower, including modalities having a lower ratio of hydrogen peroxide compared to other peroxycarboxylic acids, and additional hydrogen peroxide can be added to the methods. In this regard, the ratio of peroxyformic acid to hydrogen peroxide may be at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1 , at least 10:1, at least 11:1, at least 12:1, at least 13:1, at least 14:1, at least 15:1, at least 16:1, at least 17:1, at least at least 18:1, at least 19:1, at least 20:1, at least 21:1, at least 22:1, at least 23:1, at least 24:1, at least 25:1, at least 26 :1, at least 27:1, at least 28:1, at least 29:1 or at least 30:1 and combined with additional hydrogen peroxide added to the methods.

[0064] In one aspect, the peroxyformic acid composition is provided at an active level of from about 5 ppm to about 200 ppm, from about 5 ppm to about 100 ppm, from about 5 ppm to about 80 ppm, from about 10 ppm to about 80 ppm, or preferably from about 20 ppm to about 80 ppm. In more preferred embodiments, the peroxyformic acid composition is provided at an active level of from about 5 ppm to about 80 ppm, or about 5 ppm to about 40 ppm. In a beneficial aspect of the methods described herein, the peroxyformic acid composition can be dosed at a lower active level compared to other peroxycarboxylic acid compositions, such as peroxyacetic acid. This is a benefit to methods, as the higher antimicrobial activity of the peroxyformic acid composition allows the use of a lower amount of the peroxycarboxylic acid and therefore overcomes the lower pKa of the acid, which is often a disadvantage of a method. washing process that requires a step of neutralizing the acid with a source of alkalinity. Peroxyformic acid compositions can be generated through the reaction of an ester of a polyhydric alcohol and formic acid and hydrogen peroxide or a substance that generates hydrogen peroxide when in contact with a liquid, as disclosed in US Patent 9,518. 013, which is incorporated by reference. Peroxyformic acid compositions can also be generated through a reaction of formic acid and hydrogen peroxide or a substance that generates hydrogen peroxide when in contact with a liquid, as disclosed in US Patent Publication 2016/0176814, which is incorporated by reference. Various reactions to generate peroxyformic acid (alone or in combination with additional peracids) can be achieved through the use of on-site generators, including those disclosed in US Patents 8,858,895 and 9,192,909 and US Patent Publication 2017/0064949 incorporated by reference .

Peroxyformic Acid Generated with Formic Acid

[0065] Peroxyformic acid compositions can be generated through the reaction of formic acid and hydrogen peroxide or a substance that generates hydrogen peroxide when in contact with a liquid. A method of forming peroxyformic acid comprises contacting formic acid with hydrogen peroxide to form a resultant aqueous composition comprising a peracid comprising peroxyformic acid, wherein prior to said contacting, the ratio of the concentration of said formic acid (w/v) and the concentration of said hydrogen peroxide (w/v) is about 2 or more and the ratio of the concentration of said peracid (w/w) to the concentration of hydrogen peroxide (w/w) in said aqueous composition resultant formed reaches about 2 or higher at least within 4 hours, or preferably 2 hours after said contact. Formic acid can be supplied in any suitable manner. In some embodiments, prior to the contacting step, the formic acid may be provided in a composition comprising formic acid, for example, an aqueous solution comprising formic acid. In other embodiments, prior to the contacting step, the formic acid can be provided in a composition comprising a substance that generates formic acid on contact with an aqueous composition. Any suitable substance which generates formic acid can be used in the present methods. The substance may be a formate salt, for example a sodium or ammonium formate salt, or a formate ester. Exemplary formate esters include glycerol formates, pentaerythritol formates, mannitol formates, propylene glycol formates, sorbitol formates and sugar formates. Exemplary sugar formats include sucrose formats, dextrin formats, maltodextrin formats and starch formats. In some embodiments, the formats may be provided in a solid composition, such as a starch format.

[0066] The hydrogen peroxide used in the present methods may be provided in any suitable manner. In some embodiments, prior to the contacting step, the hydrogen peroxide may be provided in a composition comprising hydrogen peroxide, for example, an aqueous solution comprising hydrogen peroxide. In other embodiments, prior to the contacting step, the hydrogen peroxide may be provided in a composition comprising a substance which generates hydrogen peroxide upon contact with an aqueous composition. Any suitable substance that generates hydrogen peroxide can be processed in the present methods. The substance may comprise a hydrogen peroxide precursor. Any suitable hydrogen peroxide precursor can be used in the present methods. For example, the hydrogen peroxide precursor can be sodium percarbonate, sodium perborate, ureic hydrogen peroxide, or PVP hydrogen peroxide.

[0067] In some embodiments, formic acid provided in a first aqueous composition is contacted with hydrogen peroxide provided in a second aqueous composition to form peroxyformic acid in the resulting aqueous composition. In other embodiments, formic acid provided in a first aqueous composition is contacted with a substance which generates hydrogen peroxide upon contact with an aqueous composition provided in a second solid composition to form peroxyformic acid in the resulting aqueous composition. In still other embodiments, a substance that generates formic acid upon contact with an aqueous composition provided in a first solid composition is contacted with hydrogen peroxide provided in a second aqueous composition to form peroxyformic acid in the resulting aqueous composition. In still other embodiments, a substance that generates formic acid upon contact with an aqueous composition provided in a first solid composition and a substance that generates hydrogen peroxide upon contact with an aqueous composition provided in a second solid composition is contacted with a third aqueous composition to form peroxyformic acid in the resulting aqueous composition. In still other embodiments, a substance that generates formic acid upon contact with an aqueous composition and a substance that generates hydrogen peroxide upon contact with an aqueous composition are provided in a first solid composition, and the first solid composition is contacted with a second composition. aqueous to form peroxyformic acid in the resulting aqueous composition. The resulting aqueous composition comprising a peracid comprising peroxyformic acid can be any suitable type of aqueous compositions. For example, the resulting aqueous composition can be an aqueous solution. In another example, the resulting aqueous composition can be an aqueous suspension.

[0068] Before the contacting step, the ratio between the formic acid concentration (w/v) and the hydrogen peroxide concentration (w/v) can be in any suitable range. In some embodiments, prior to contacting, the ratio of the formic acid concentration (w/v) to the hydrogen peroxide concentration (w/v) may be from about 2 to about 100, for example about 2 to 3, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 15, 15 to 20, 20 to 25, 25 to 30, 30 to 35 , 35 to 40, 40 to 45 or 45 to 50 or more than about 50 to 100. The ratio of the peracid concentration (w/w) to the hydrogen peroxide concentration (w/w) in the aqueous composition formed can reach any suitable range. In some embodiments, the ratio between the peracid concentration (w/w) and the hydrogen peroxide concentration (w/w) in the formed aqueous composition can reach, within about 4 hours or, preferably, 2 hours of contact , about 2 to about 1,500, for example, about 2 to 3, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 15, 15 to 20, 20 to 25, 25 to 30, 30 to 35, 35 to 40, 40 to 45, 45 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, 90 to 100, 100 to 200, 200 to 300, 300 to 400, 400 to 500, 500 to 600, 600 to 700, 700 to 800, 800 to 900, 900 to 1,000, 1,000 to 1,100, 1,100 to 1,200, 1,200 to 1,300 or 1,300 to 1,340 1,400 to 1,500. In other embodiments, the ratio between the peracid concentration (w/w) and the hydrogen peroxide concentration (w/w) in the formed aqueous composition reaches at least about 10 within about 30 minutes of contact, from preferably at least about 10 to 40 within about 30 minutes of contact.

[0069] The aqueous composition formed may comprise any suitable concentration of hydrogen peroxide. In some embodiments, the aqueous composition formed can comprise about 5% (w/w) or less hydrogen peroxide, for example, about 5% (w/w), 4.5% (w/w), 4 % (w/w), 3.5% (w/w), 3% (w/w), 2.5% (w/w), 2% (w/w), 1.5% (w/w) p), 1% (w/w), 0.9% (w/w), 0.8% (w/w), 0.7% (w/w), 0.6% (w/w) , 0.5% (w/w), 0.4% (w/w), 0.3% (w/w), 0.2% (w/w), 0.1% (w/w) , 0.05% (w/w), 0.01% (w/w), 0.005% (w/w) or 0.001% (w/w) hydrogen peroxide. In other embodiments, the formed aqueous composition reaches about 2% (w/w) or less hydrogen peroxide within at least about 4 hours, or preferably 2 hours of contact. In still other embodiments, the aqueous composition formed reaches about 1% (w/w) or less hydrogen peroxide within at least about 1 hour of contact. In still other embodiments, the aqueous composition formed achieves about 0% (w/w) to about 0.001% (w/w) hydrogen peroxide and maintains about 0% (w/w) to about 0.001% ( w/w) of hydrogen peroxide for at least 1 hour.

[0070] The present methods can be conducted in the presence of a catalyst. Any suitable catalyst can be used in the present methods. In some embodiments, the catalyst can be a mineral acid, for example, sulfuric acid, methanesulfonic acid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid or phosphonic acid. The present methods can also be conducted in the presence of a cationic acid exchange resin system. Any suitable cationic acid exchange resin system can be used in the present methods. In some embodiments, the cationic acid exchange resin system is a strong cationic acid exchange resin system. In other embodiments, the acid exchange resin system is sulfonic acid exchange resin, for example, commercially available as Dowex M-31 or Nafion.

[0071] The resulting aqueous composition may comprise a stabilizing agent for the peracid. Any suitable stabilizing agents can be used in the present methods. Exemplary stabilizing agents include phosphonate salt(s) and/or a heterocyclic dicarboxylic acid, for example dipicolinic acid.

[0072] The present methods may additionally comprise a step of reducing the concentration of hydrogen peroxide in the resulting aqueous composition. The concentration of hydrogen peroxide in the resulting aqueous composition can be reduced using any suitable methods. For example, the concentration of hydrogen peroxide in the resulting aqueous composition can be reduced using a catalase or a peroxidase. Peroxyformic Acid Generated with Esters of a Polyhydric Alcohol and Formic Acid

[0073] Peroxyformic acid compositions can be generated through the reaction of an ester of a polyhydric alcohol and formic acid and hydrogen peroxide or a substance that generates hydrogen peroxide when in contact with a liquid. Peroxyformic acid forming compositions according to the methods comprise: a) a first reagent comprising an ester of a polyhydric alcohol and formic acid; and b) a second reagent comprising hydrogen peroxide or comprising a substance which generates hydrogen peroxide when in contact with a liquid, wherein 1) said first reagent and said second reagent are kept separately prior to use, and when it is At the time of generating peroxyformic acid, said first reagent and said second reagent are arranged to be contacted with each other to form a liquid comprising peroxyformic acid and having a pH below about 11, and the pH of the formed liquid is at about 8 or less within about 1 minute after contact between said first reagent and said second reagent; or 2) said second reagent comprises a substance which generates hydrogen peroxide when in contact with a liquid, said first reagent and said second reagent are comprised of a solid composition and, when it is time to generate peroxyformic acid, said composition solid is configured to be contacted with a liquid to form a liquid that comprises peroxyformic acid and has a pH below about 11, and the pH of the formed liquid becomes about 8 or less within about 1 minute after contact between said solid composition and said liquid.

[0074] The present peroxyformic acid-forming compositions may comprise any suitable ester of a polyhydric alcohol and formic acid. Typically, a polyhydric alcohol refers to a molecule with two or more hydroxyl (-OH) groups. An ester of a polyhydric alcohol and formic acid refers to an ester formed between a polyhydric alcohol and formic acid. Esters, as referred to herein, are considered 'waterless' systems as no additional water is added to the reaction. In some embodiments, the present peroxyformic acid-forming compositions comprise glycerol formates, pentaerythritol formates, mannitol formates, propylene glycol formates, sorbitol formates and sugar formates. The present peroxyformic acid forming compositions may comprise any suitable sugar formates, for example sucrose formates, dextrin formates, maltodextrin formates or starch formates.

[0075] In a preferred embodiment, a liquid reaction employs glycerol formates, pentaerythritol formates, mannitol formates, or propylene glycol formates. In yet another preferred embodiment, a liquid reaction employs glycerol formates. Beneficially, the glycerol formates rapidly undergo hydrolysis to generate peroxyformic acid according to the methods. In one aspect, the provided precursors do not include additional water added to the system, which would negatively interfere with the kinetics of the reaction between the ester of a polyhydric alcohol and formic acid and formic acid and hydrogen peroxide. In one aspect, the premixes and peroxyformic acid-forming composition do not add free water to the systems, which would negatively interfere with ester, e.g., glycerol formates.

[0076] In a preferred embodiment, a solid reaction employs sugar formates, for example sucrose formates, dextrin formates, maltodextrin formates or starch formates. In yet another preferred embodiment, a solid reaction employs starch formates.

[0077] The present peroxyformic acid-forming compositions may comprise a use solution or a concentrate of the ester of a polyhydric alcohol and formic acid. In some aspects, the methods generate a peroxyformic acid through a reaction of an ester concentrate of a polyhydric alcohol and formic acid. In other aspects, the methods generate a peroxyformic acid through a reaction of dilute use solution of the ester of a polyhydric alcohol and formic acid.

[0078] The first or second reagent may have any suitable pH range in the present peroxyformic acid-forming compositions. For example, the first or second reagent can have a pH below 11, or from about -2 to about 11, or from about 0 to about 11, for example, about -2 to about -1 , -2 to about 0, 0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0- 11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3- 9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 611, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11 or about -2, -1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the first or second reagent has a pH ranging from about 5 to about 10, for example, about 5-6, 5-7, 5-8, 5-9 , 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10 or 9-10. In other embodiments, the first or second reagent has a pH of about 9.

[0079] The first reagent and the second reagent may be configured to be contacted together to form a liquid, for example, a solution comprising peroxyformic acid and having any suitable pH, including a pH below 11, or about - 2 to about -2 to about 11, or from about 0 to about 11, for example, about -2 to about -1, -2 to about 0, 0-1, 0-2, 0 -3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 12, 1-3, 1-4, 1-5, 1 -6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9 , 2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4 -7, 4-8, 4-9, 410, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6 -9, 6-10, 6-11, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11 , 10-11 or about -2, -1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example a solution comprising peroxyformic acid and having a pH ranging from about -2 to about 11, 0 to about 10 or 5 to about 10, for example about -2-0, 0-1, 1-2, 2-3, 3-4, 4-5, 5-6, 5-7, 5-8, 5-9, 510, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, 9-10 or 10-11. In other embodiments, the first reagent and the second reagent are arranged to be contacted together to form a liquid, for example, a solution comprising peroxyformic acid and having a pH of about 9. In a preferred aspect, the liquid formed, for example, a solution comprising peroxyformic acid and having a nearly neutral pH of about 6-7.

[0080] The pH of the liquid formed can be about 8 or lower within about 1 minute after contact between the first reagent and the second reagent or after contact between the solid composition and the liquid. In some embodiments, the pH of the liquid formed can be about 8 or lower within about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds after contact between the first reagent and the second reagent or after contact between the solid composition and the liquid. In other embodiments, the pH of the formed liquid comprising peroxyformic acid drops to about 8 or lower within about 1 minute or less. In one aspect, the pH of the liquid formed comprising peroxyformic acid is about 8 or lower within about 45 seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds or less, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5 seconds or less. In one aspect, the pH of the formed liquid comprising peroxyformic acid drops to about 8 or lower almost instantly. In other embodiments, the pH of the liquid formed can be about lower than -2, -1, 0, 1, 2, 3, 4, 5, 6, 7 or 8 within about 1 minute after contact between the first reagent and the second reagent or after contact between the solid composition and the liquid.

[0081] The liquid comprising peroxyformic acid can maintain the pH ranging from about -2 to about 8, or from about 0 to about 8 for any suitable time after contact between the first reagent and the second reagent, or after contact between the composition and a liquid. In some embodiments, the liquid comprising peroxyformic acid maintains a pH ranging from about -2 to about 8, or from about 0 to about 8 from about 1 second to about 10 hours after contact between the first reactant and and the second reagent or after contact between the composition and a liquid. For example, the liquid comprising peroxyformic acid can maintain the pH at about -2, -1, 0, 1, 2, 3, 4, 5, 6, 7 or 8 from about 1 second to about 10 hours after contact between the first reagent and the second reagent or after contact between the composition and a liquid. In another example, the liquid comprising peroxyformic acid can maintain the pH ranging from about 0 to about 8 for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 20 minutes , 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours. In a preferred aspect, the liquid formed, for example, a solution comprising peroxyformic acid and having a near neutral pH of about 6-7 in a use solution.

[0082] In some embodiments, the first reagent and the second reagent are configured to be contacted together to form a solution comprising peroxyformic acid and having a pH ranging from about 4 to about 8 or 9, for example about 4-5, 5-6, 6-7, 7-8 or 8-9. In a preferred aspect, the liquid formed, for example, a solution comprising peroxyformic acid and having a near neutral pH of about 6-7 in a use solution. In one example, the first reagent and the second reagent are configured to be contacted together to form a solution that comprises peroxyformic acid and has a pH ranging from about 6 to about 8 or 9. The first reagent and the second reagent can be arranged to be contacted together to form a solution comprising peroxyformic acid and having a pH ranging from about 4 to about 8 or 9, and the solution may maintain the pH range for any suitable amount of time, for example, from about 1 minute to about 24 hours. For example, the solution can maintain the pH range from about 4 to about 8 or 9 for at least 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes , 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.

[0083] In other embodiments, the solid composition is configured to be contacted with a liquid to form a solution comprising peroxyformic acid and having a pH ranging from about 4 to about 8 or 9, for example about 4-5 , 5-6, 6-7, 7-8 or 8-9. In one example, the solid composition is configured to be contacted with a liquid to form a solution that comprises peroxyformic acid and has a pH ranging from about 6 to about 8 or 9. The solid composition is configured to be contacted with a liquid to form a solution comprising peroxyformic acid and having a pH ranging from about 4 to about 8 or 9, and the solution may maintain the pH range for any suitable amount of time, for example, from about 1 minute to about 24 hours. For example, the solution can maintain the pH range from about 4 to about 8 or 9 for at least 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes , 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours. In a preferred aspect, the liquid formed, for example, a solution comprising peroxyformic acid and having a near neutral pH of about 6-7 in a use solution.

[0084] The first reagent and the second reagent may be arranged to be contacted with each other to form a liquid, for example, a solution comprising peroxyformic acid under any suitable conditions or temperature. In some embodiments, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example, a solution, comprising peroxyformic acid under ambient conditions. In other embodiments, the first reagent and the second reagent are arranged to be contacted together to form a liquid, for example a solution comprising peroxyformic acid, at a temperature ranging from about -2oC to about 60oC, 0 o o o o oo C to about 60 C, or 4 C to about 60 C, for example, about -2 C-0 C, oo oo oo o o o o o o o o o 0 C-4 C, 4 C-5 C, 4 C-5 C, 5 C-10 C, 10 C-15 C, 15 C-20 C, 20 C-25 C, oo oo oo oo oo oo 25 C-30 C, 30 C-35 C, 35 C-40 C, 40 C -45C, 45C-50C, 50C-55C, or 55oC-60oC. In still other embodiments, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example, a solution comprising peroxyformic acid at a temperature of about 4°C or less than 4°C, for example, about 3oC, 2oC, 1oC, 0oC or less than 0oC.

[0085] The solid composition may be configured to be contacted with a liquid to form a liquid, for example a solution comprising peroxyformic acid under any suitable conditions or temperature. In some embodiments, the solid composition can be configured to be contacted with a liquid to form a liquid, for example, a solution comprising peroxyformic acid under ambient conditions. In other embodiments, the solid composition may be configured to be contacted with a liquid to form a liquid, for example a solution comprising peroxyformic acid, at a temperature ranging from about -2°C to about 60°C, 0°C to about 60°C , o o oo oo oo or 4 C at about 60 C, for example about -2 C-0 C, 0 C-4 C, 4 C-5 C, oo o o o o o o o o o o o o 4 C-5 C, 5 C-10 C, 10C-15C, 15C-20C, 20C-25C, 25C-30C, 30C oo oo oo oo oo 35C, 35C-40C, 40C-45C, 45C -50C, 50C-55C, or 55C-60C. In still other embodiments, the solid composition may be configured to be contacted with a liquid to form a liquid, for example, a solution comprising peroxyformic acid at a temperature of about 4°C or oooooo less than 4°C, for example about 3°C, 2°C, 1°C, 0°C or less than 0°C.

[0086] The present peroxyformic acid-forming compositions may further comprise a catalyst (e.g., mineral acid) or an enzyme that catalyzes the formation of peroxyformic acid from the ester of a polyhydric alcohol and formic acid, and hydrogen peroxide. The present peroxyformic acid forming compositions may comprise any suitable catalyst, for example a strong mineral acid or enzyme, for example a perhydrolytic enzyme, lipase, coronase, termanyl or ewaitase. The catalyst or an enzyme may be comprised in any suitable part of the present peroxyformic acid-forming compositions. In some embodiments, the first reactant comprises the catalyst or enzyme. In other embodiments, the second reagent comprises the catalyst or enzyme. In yet other embodiments, the present peroxyformic acid-forming compositions can further comprise a third reagent comprising the catalyst or enzyme. In still other embodiments, the solid composition comprises the catalyst or enzyme.

[0087] The present peroxyformic acid-forming compositions may further comprise a stabilizing agent for peroxyformic acid, a stabilizing agent for hydrogen peroxide and/or a pH buffering agent. In one aspect, the stabilizing agent(s) and/or pH buffering agents are useful in lowering the pH of the compositions to neutral pH or lower. The present peroxyformic acid-forming compositions may comprise any suitable stabilizing agent. Exemplary stabilizing agents include phosphonate salt(s) and/or a heterocyclic dicarboxylic acid, for example dipicolinic acid. In some embodiments, the stabilizing agent is pyridine carboxylic acid-based stabilizers such as picolinic acid and salts, pyridine-2,6-dicarboxylic acid and salts, and phosphonate-based stabilizers such as phosphoric acid and salts, pyrophosphoric acid and salts and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts. In other embodiments, the present peroxyformic acid-forming compositions comprise two or more stabilizing agents, for example, HEDP and 2,6-pyridinedicarboxylic acid (DPA). The stabilizing agent(s) may be comprised in any suitable part of the present peroxyformic acid-forming compositions. In some embodiments, the first reagent comprises a stabilizing agent for peroxyformic acid and/or a pH buffering agent. In other embodiments, the second reagent comprises a stabilizing agent for hydrogen peroxide. In still other embodiments, the present peroxyformic acid-forming compositions can further comprise a third reagent comprising a stabilizing agent for peroxyformic acid, a stabilizing agent for hydrogen peroxide, and/or a pH buffering agent. In still other embodiments, the solid composition comprises a peroxyformic acid stabilizing agent, a hydrogen peroxide stabilizing agent, and/or a pH buffering agent.

[0088] The present peroxyformic acid-forming compositions may comprise any suitable pH buffering agent. The pH buffer reagent can include any reagent that is compatible with the ester(s) in the present peroxyformic acid-forming compositions. Exemplary buffering agents suitable for use with a liquid ester can be an organic amine such as triethanol amine, imidazole, etc. Exemplary buffering agents suitable for use with a solid form of ester include a broader range of buffers, such as a carbonate salt, a phosphate salt, and the like. The pH buffering reagent can be comprised in any suitable part of the present peroxyformic acid-forming compositions. In some embodiments, the first reagent comprises a pH buffering agent. In other embodiments, the present peroxyformic acid-forming compositions can further comprise a third reagent comprising a pH buffering agent. In still other embodiments, the solid composition comprises a pH buffering agent.

[0089] The present peroxyformic acid-forming compositions may comprise any suitable stabilizing agent for hydrogen peroxide. Exemplary stabilizing agents for hydrogen peroxide include phosphonates, heterocyclic carboxylic acids and mixtures thereof. In some embodiments, the stabilizing agents for hydrogen peroxide can be Dequest 2010, Dequest 2066, Dipicolinic acids, etc. The stabilizing agent for hydrogen peroxide can be comprised in any suitable part of the present peroxyformic acid-forming compositions. In some embodiments, the second reagent comprises a stabilizing agent for hydrogen peroxide. In other embodiments, the present peroxyformic acid-forming compositions can further comprise a third reagent comprising a stabilizing agent for hydrogen peroxide. In still other embodiments, the solid composition comprises a stabilizing agent for hydrogen peroxide.

[0090] The present peroxyformic acid-forming compositions may comprise any suitable concentration of an ester of a polyhydric alcohol and formic acid. For example, the first reagent of the peroxyformic acid-forming composition can comprise any suitable concentration of an ester of a polyhydric alcohol and formic acid. In some embodiments, the liquid formed is a concentrate and comprises the first reactant in an amount of up to about 90% of an ester of a polyhydric alcohol and formic acid. In other embodiments, the liquid formed comprises the first reactant in an amount of from about 1 ppm to about 500,000 ppm of an ester of a polyhydric alcohol and formic acid, or from about 10 ppm to about 500,000 ppm of a ester of a polyhydric alcohol and formic acid. For example, the first reagent in the formed liquid may comprise of about 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70 -80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450 -500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, 950 -1,000 ppm, 1,000-1.500 ppm, 1,500-2,000 ppm, 2,000-2.500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5.500 ppm, 5,500 -6,000 ppm, 6,000-6.500 ppm, 6,500-7.000 ppm, 7,000-7.500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm, 30,000 -40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm, 200,000250,000 ppm, 250,000 -300,000 ppm, 300,000-350,000 ppm, 350,000- 400,000 ppm, 400,000-450,000 ppm or 450,000-500,000 ppm. In other embodiments, the first reactant in the liquid formed can comprise from about 50 ppm to about 40,000 ppm of an ester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500, 50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000, 50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000 or 50-40,000 ppm of a ester of a polyhydric alcohol and formic acid.

[0091] In another example, the solid composition of the peroxyformic acid-forming composition may comprise any suitable concentration of an ester of a polyhydric alcohol and formic acid. In some embodiments, the solid composition can provide a concentrated formed liquid comprising the first reactant in an amount of up to about 90% of an ester of a polyhydric alcohol and formic acid. In other embodiments, the solid composition can provide the liquid formed from about 10 ppm to about 500,000 ppm of an ester of a polyhydric alcohol and formic acid. For example, the solid composition can provide the liquid formed the ester of a polyhydric alcohol and formic acid in amounts ranging from about 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40- 50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300- 350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800- 850 ppm, 850-900 ppm, 900-950 ppm, 950-1000 ppm, 1000-1500 ppm, 1500-2000 ppm, 2000-2500 ppm, 2500-3000 ppm, 3000-3500 ppm, 3500 ppm-4000 ppm. , 4,500-5.000 ppm, 5,000-5.500 ppm, 5,500-6,000 ppm, 6,000-6.500 ppm, 6,500-7,000 ppm, 7,000-7.500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm , 10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, 90,000100,000 ppm, 100,000-150,000 ppm , 150,000-200,000p pm, 200,000-250,000 ppm, 250,000-300,000 ppm, 300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm or 450,000-500,000 ppm. In other embodiments, the solid composition can provide the liquid formed from about 50 ppm to about 40,000 ppm of an ester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500, 50-1,000, 50-1500, 50-2000, 50-2500, 503000, 50-3500, 50-4000, 50-4500, 50-5000, 50-10000, 50-20000, 50-30000 or 50-40000 ppm ester a polyhydric alcohol and formic acid.

[0092] The present peroxyformic acid-forming compositions may comprise any suitable concentration of hydrogen peroxide or a substance which generates hydrogen peroxide on contact with a liquid. For example, the second reagent of the peroxyformic acid-forming composition can comprise any suitable concentration of hydrogen peroxide. In some embodiments, a liquid formed concentrate comprises the second reactant in an amount of up to about 10% hydrogen peroxide. In some embodiments, the formed liquid comprises the second reactant in an amount comprising about 0.1 ppm to about 100,000 ppm hydrogen peroxide, or about 0.1 ppm to about 100,000 ppm hydrogen peroxide. For example, the second reagent in the formed liquid may comprise of about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60 -70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400 -450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, 9501,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm, 2,500,3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm, 4,500 ppm, 5,000 ppm 5,500-6,000 ppm, 6,000-6,500 ppm, 6,5007,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm, 8,500 9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm, 30,000 -40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or 90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm, 200,000-250,000 ppm or 250,000-300,000 ppm of hydroxy peroxide rogen. In other embodiments, the second reagent in the formed liquid comprises from about 150 ppm to about 50,000 ppm of hydrogen peroxide, for example, about 150-200, 150-300, 150-400, 150-500, 150-600 . -10,000, 50-20,000, 50-30,000, 50-40,000 or 50-50,000 ppm of hydrogen peroxide.

[0093] In some embodiments, a liquid formed concentrate comprises the second reactant in an amount of up to about 10% hydrogen peroxide. In another example, the solid composition can comprise a substance in an amount or concentration that generates from about 0.1 ppm to about 100,000 ppm of hydrogen peroxide upon contact with a liquid in the formed liquid. For example, the solid composition can comprise a substance in an amount or concentration that yields from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4.00 ppm, 4.00 ppm 4,500-5.000 ppm, 5,000-5.500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or 90,000-100,000 ppm of hydrogen peroxide.

[0094] The present peroxyformic acid-forming compositions may be configured to form a liquid, for example a solution, comprising any suitable concentration of peroxyformic acid. For example, the first reagent and the second reagent in the present peroxyformic acid-forming compositions may be configured to be contacted together to form a liquid and/or solid, for example, a solution comprising any suitable concentration of peroxyformic acid. In some embodiments, the first reagent and the second reagent can be arranged to be contacted together to form a liquid, for example, a solution comprising from about 0.1 ppm to about 100,000 ppm peroxyformic acid, from about 0.1 ppm to about 10,000 ppm peroxyformic acid or from about 0.1 ppm to about 5,000 ppm peroxyformic acid, e.g. about 0.1-1 ppm, 1-10 ppm, 10-20 ppm , 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm , 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700 -750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,00 -3500 ppm, 3500-4000 ppm, 4000-4500 ppm or 4500-5000 ppm or greater peroxyformic acid. In other embodiments, the first reagent and the second reagent can be arranged to be contacted together to form a liquid, for example, a solution comprising from about 1 ppm to about 500 ppm of peroxyformic acid, for example, about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm, 0.1-30 ppm, 0.1-40 ppm, 0.1-50 ppm, 0.1-60 ppm, 0 .1-70 ppm, 0.1-80 ppm, 0.1-90 ppm, 0.1-100 ppm, 0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0, 1-300 ppm, 0.1-350 ppm, 0.1-400 ppm, 0.1-450 ppm, 0.1-500 ppm peroxyformic acid. In still other embodiments, the first reagent and the second reagent can be arranged to be contacted together to form a liquid, for example, a solution, comprising from about 50 ppm to about 100 ppm of peroxyformic acid, for example, about 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm or 90-100 ppm peroxyformic acid. In still other embodiments, the first reagent and the second reagent can be arranged to be contacted together to form a liquid, for example, a solution, comprising from about 200 ppm to about 300 ppm of peroxyformic acid, for example, about 200-210 ppm, 210-220 ppm, 220-230 ppm, 230-240 ppm, 240-250 ppm, 250-260 ppm, 260-270 ppm, 270-280 ppm, 280-290 ppm, 290-300 ppm of peroxyformic acid.

[0095] The present peroxyformic acid-forming compositions can be configured to form a liquid, for example a solution, comprising any suitable concentration of peroxyformic acid within any suitable time. For example, the first reagent and the second reagent in the present peroxyformic acid-forming compositions can be configured to be contacted together to form a liquid and/or solid, for example, a solution comprising any suitable concentration of peroxyformic acid within any suitable time. In some embodiments, the first reagent and the second reagent can be arranged to be contacted together to form a liquid, for example, a solution, comprising at least about 1 ppm of peroxyformic acid within 1 minute of the contact time, for example, at least about 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, or 5000 ppm or more of peroxyformic acid within 1 minute of contact time.

[0096] In one aspect, at least about 1 ppm of peroxyformic is generated within less than 1 minute of contacting the first reagent and the second reagent. In one aspect, at least about 1 ppm of peroxyform is generated in less than about 55 seconds, 50 seconds or less, 45 seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5 seconds or less. In one aspect, the reaction to form a liquid comprising at least about 1 ppm of peroxyformic acid is nearly instantaneous. In one aspect, at least about 100 ppm or at least about 500 ppm of peroxyformic is generated within about 5 minutes or less of contacting the first reagent and the second reagent. In one aspect, at least about 100 ppm or 500 ppm of peroxyformic is generated within less than about 4 minutes, 3 minutes or less, 2 minutes or less, or 1 minute or less.

[0097] The present peroxyformic acid-forming compositions can be configured to form a liquid, for example, a solution, comprising any suitable percentage of the peak concentration of peroxyformic acid within any suitable time. For example, the first reagent and second reagent in the present peroxyformic acid-forming compositions can be configured to be contacted together to form a liquid, for example, a solution comprising any suitable percentage of the peak concentration of peroxyformic acid within any suitable time. In some embodiments, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example, a solution comprising at least about 80% of the peak concentration of peroxyformic acid within about 5 minutes at about 15 minutes of contact time. For example, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example, a solution, comprising at least about 80%, 85%, 90%, 95%, 96%, 97 %, 98%, 99% or 100% of the peak peroxyformic acid concentration within about 5 minutes to about 15 minutes of contact time. In another example, the first reagent and the second reagent are configured to be contacted together to form a liquid, for example, a solution, comprising at least about 80% of the peak concentration of peroxyformic acid within about 5. 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 minutes of contact time.

[0098] The peroxyformic acid formed can maintain any suitable percentage of the peak concentration of peroxyformic acid within any suitable time. In some embodiments, the peroxyformic acid formed can maintain at least about 50% of the peak concentration from about 5 minutes to about 25 minutes after contact between the first reagent and the second reagent or after contact between the solid composition and a liquid. For example, the peroxyformic acid formed can maintain at least about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98 %, 99%, or 100% of the peak concentration from about 5 minutes to about 25 minutes after contact between the first reagent and the second reagent or after contact between the solid composition and a liquid. In another example, the peroxyformic acid formed can maintain at least about 50% of the peak concentration for about 5-25 minutes, for example, about 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 minutes, after contact between the first reagent and the second reagent or after contact between the solid composition and a liquid. In preferred aspects of the methods the desired peak concentration of peroxyformic acid is 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm , 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 5000 ppm, 6000 ppm, 7000 ppm, 8000 ppm, 9. 10,000 ppm or more (including all tracks in them).

[0099] The present peroxyformic acid forming compositions may further comprise a C2-C22 percarboxylic acid and wherein the first reagent or the solid composition comprising the first reagent and the second reagent are maintained separately from the C2-C22 percarboxylic acid before generating acid peroxyformic. The present peroxyformic acid-forming compositions may comprise any suitable C2-C22 percarboxylic acid, for example peroxyacetic acid, peroxyethanolic acid and/or peroxysulfonated oleic acid. In one aspect, additional peroxycarboxylic acid compositions can be employed in combination with the peroxyformic acid composition. For example, C1-C24 peroxycarboxylic acid, C1-C24 peroxycarboxylic acid salt, C1-C24 peroxycarboxylic acid ester, or mixtures thereof. A carboxylic acid is an organic acid (R-COOH) that contains an aliphatic group and one or more carboxyl groups. A carboxyl group is represented by -COOH and is usually located at the terminal end of the acid. The aliphatic group can be a substituted or unsubstituted group. Aliphatic substituents can include -OH, -OR, -NO2, halogen and the other common substituents in these groups. An example of a simple carboxylic acid is acetic acid, which has the formula CH3COOH. A peroxycarboxylic acid is a carboxylic acid that has been oxidized to contain a terminal -COOOH group. The term peroxy acid is often used to represent a peroxycarboxylic acid. An example of a simple peroxy acid is peroxyacetic acid, which has the formula CH3COOOH.

Bleaching Component

[00100] The bleaching component for the methods includes an active halogen source or a halogen-releasing substance suitable for releasing active halogen species, such as free elemental halogen (Cl, Br, Cl2, Br2) or --OCl- or --OBr-, under conditions commonly used in detergent bleaching cleaning processes of a variety of cleaning targets. Preferably, the halogen-releasing compound releases chlorine species. Chlorine-releasing compounds include potassium dichloroisocyanurate, sodium dichloroisocyanurate, chlorinated trisodium phosphate, sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, monochloramine, dichloramine, [(monotrichlor)-tetra(monopotassium dichloro)] pentaisocyanurate, 1,3- dichloro-5,5 dimethylidantonone, paratoluene sulfodichloroamide, trichloromelamine, N-chloramine, N-chlorosuccinimide, N,N'-dichloroazodicarbonamide, N-chloroacetylurea, N,N-dichlorobiuril, chlorinated dicyandiamide, trichlorocyanuric acid, dichloroglycorea, etc. . Chlorinated isocyanurate materials including dichloroisocyanurate dihydrate, sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc. are preferred sources of chlorine.

[00101] In another aspect, chlorine bleaches can be used in combination with N,N,N',N'-tetraacetylethylenediamine (TAED)/perborate for bleaching properties. In some aspects, a bleach activator and/or bleach catalyst may be employed.

Whitening Activators

[00102] The antimicrobial activity and/or bleaching activity of the methods is enhanced by the addition of a material which, when the composition is put into use, reacts or in some way interacts to form an activated component. For example, in some embodiments, a peracid or peracid salt can be formed. For example, in some embodiments, tetraacetylethylene diamine can be included within the composition to react with active oxygen to form a peracid or a peracid salt that acts as an antimicrobial and bleaching agent. Other examples of active oxygen activators include compounds containing a carboxylic, nitrile, or ester moiety, or other such compounds known in the art. Additional exemplary activators include sodium nonanoyloxybenzene sulfonate (NOBS), acetyl caprolactone and N-methyl morpholinium acetonitrile and salts thereof (such as Sokalan BMG from BASF). Bleaching Catalysts

[00103] In some embodiments, the whitening activity of the treatment compositions can be enhanced by the addition of a material which, when the composition is put into use, reacts or otherwise interacts to form an activated component. For example, in some embodiments, transition metal catalysts, especially those with iron or manganese, can be used. Surrounding the metals are ligands that typically contain nitrogen or oxygen. Effective linker structures include 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN), 1,2,-bis-(4,7,-dimethyl-1,4,7,-triazacyclonon- 1-yl)-ethane (Me4-DTNE), N,N',N"-tris[salicylidenaminoethyl]amine (saltren), macrocyclic tetraamido ligand (TAML), bispyridyl pyrimidine and terpyridine ligands. Transition metal catalysts especially preferred are manganese-containing compounds sold commercially under the names Dragon and Pegasus by Catexel. In some embodiments, instead of adding a preformed catalyst, the binders can optionally be prepared without metal. When added to the wash bath, they can combine with metal ions naturally present in the wash water, or metal ions that have been intentionally added to form a more active bleaching species in situ in the wash bath. Even in systems where there are no trace metal ions present in the water, these ligands can bind to the metal ions present in the stain, pa Enhanced stain removal.

[00104] In a preferred aspect, the catalyst is a manganese-containing compound sold commercially under the names Dragon and Pegasus by Catexel.

[00105] It is known that organic compounds can act catalytically to improve bleaching performance without combining with metal ions present either in the wash water or in the stain itself. Two general classes of such molecules are dioxiranes and oxaziridines. They are often formed in situ by oxidation of ketones and imines, respectively. Dihydroisoquinoline derivatives are an especially preferred class of molecules formed in this way.

Adjuvant and Additional Functional Ingredients

[00106] The components for antimicrobial, disinfectant and bleaching laundry methods can be further combined with various functional components suitable for use in such applications, namely laundry applications. In some embodiments, the steps of dosing a peroxyformic acid composition, an alkalinity source, a bleach activator and/or catalyst into a detergent use solution, and optionally additional hydrogen peroxide make up a large amount, or even substantially all the total actives dosed in the washing application according to the methods. For example, in some embodiments little or no additional functional ingredients are disposed therein.

[00107] In other embodiments, additional functional ingredients may be included in the various dosing steps for the methods. Functional ingredients provide desired properties and functionality for peroxyformic acid compositions, alkalinity agents and detergent use solutions. For purposes of this application, the term "functional ingredient" includes a material that, when dispersed or dissolved in a use solution and/or concentrated, such as an aqueous solution, provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only and a wide variety of other functional ingredients could be used. For example, many of the functional materials discussed below refer to materials used in a laundry application. However, other embodiments may include functional ingredients for use in other applications.

[00108] In other embodiments, the compositions may include defoaming agents, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, rinsing aids, metal protection agents, stabilizing agents, corrosion inhibitors, additional sequestrants and/or agents chelators, fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes or couplers, buffers, solvents and the like.

[00109] All publications and patent applications in this specification are indicative of the level of common skill in the art to which this invention belongs. All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application were specifically and individually indicated as incorporated by reference.

EXAMPLES

[00110] Embodiments of the present invention are further defined in the following non-limiting Examples. It is to be understood that these Examples, while indicating certain embodiments of the invention, are provided by way of illustration only. From the above discussion and these examples, one skilled in the art can confirm the essential features of this invention and without departing from the spirit and scope thereof, can make various changes and modifications of embodiments of the invention to adapt the same to various uses and conditions. . Thus, various modifications of embodiments of the invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

EXAMPLE 1

[00111] The bleaching measurement of a laundry method was carried out using a Tergotometer with 1 L vessels and water bath. First, unwashed samples of the lot numbers to be used in the test are read on a HunterLab Color Quest spectrophotometer to establish the average starting L-value (before washing). This L-value is a measure for whiteness on a gray scale. An L value of 0 means black and an L value of 100 means white. A sampling of 25 samples of each type is typically used. Next, the desired wash temperature of 40°C (104°F) is programmed into the Tergotometer and its water bath allowed to warm up to that temperature. One liter of the water type is added to each Tergotometer vessel and allowed to equilibrate to temperature.

[00112] The tested bleaching compositions are weighed and added to the Tergotometer vessels.

[00113] The samples are then added quickly to the respective vessels, in a left-to-right sequence, in order to minimize differences in exposure time to the detergent systems. During this washing process, agitation is generally used throughout the entire process.

[00114] At the end of the run, the samples are removed from the vessels quickly in a left to right sequence using forceps, then squeezed to remove excess water, and finally left to air dry.

[00115] Finally, the samples are read on the HunterLab Color Quest spectrophotometer and the % dirt removal is calculated as follows: % dirt removal = (final L - initial L)/(96 - initial L) * 100 .

[00116] In this example, peracid was added initially, followed by samples and an alkaline source after 5 minutes, then followed by a manganese transition metal catalyst after 6 minutes. The Tergetometer was operated for an additional 4 minutes, bringing a total running time of 10 minutes. The tested formulations are shown in Tables 1A and 1B. The target dosage is shown in Table 2 and the results are shown in Table 3, with corresponding results represented in Figure 1. The final pH of the wash liquor was also measured and is shown in Table 4.

[00117] As shown in the tables and in FIG. 2, formulations containing low levels of hydrogen peroxide containing PFA will not have a measurable whitening effect, even if an oxygen catalyst is added to the system. The data show that a low peroxide PFA composition is not desired to neutralize alkalinity in washing methods and enhance bleaching effectiveness. However, PFA formulations containing high hydrogen peroxide with the bleaching component achieve an increase in bleaching effectiveness through the addition of an oxygen catalyst.

EXAMPLE 2

[00118] The titrations were completed using a dose of 20 ppm of PFA of the formula C in 1L of grain water 5. The addition of 5% NaOH solution was completed before the pH measurement in order to obtain the titration curve shown in Figure 2. The titration was then repeated to a PAA of 80 ppm. Both titrations were completed at room temperature. The test conditions are summarized in Table 5. The raw data corresponding to Figure 2 are shown in Table 6.

[00119] As shown in this Example, the use of an acid in the first step requires alkalinity to neutralize it. Beneficially, since peroxyformic acid compositions are effective in lower dose methods, less acid is introduced and therefore needs less alkalinity to neutralize.

EXAMPLE 3

[00120] The micro-efficacy performance comparison between PAA and PFA formulations on Klebsiella pneumoniae (ATCC 4352) was compared at a dosing temperature of 40°C for 5 minutes of contact. Three sterile samples (1”x 1.5”) were inoculated with 0.03 mL of a prepared suspension containing Klebsiella pneumoniae. The carriers were then dried to visibly dry and aseptically placed between the sixth and seventh plies of a rolled fabric spindle. The shaft was then placed in a chamber. PFA and PAA solutions were then added to the chamber (75 g). The chamber was fixed on a laundrometer and run for 5 minutes at 40°C. After 5 minutes, the carriers were neutralized separately and then diluted and coated to calculate log reductions. The wash water was also neutralized and then diluted and overlayed to calculate log reductions.

[00121] PAA was dosed at a rate labeled for tissue disinfection a (4 oz/cwt; 60 gal/cwt for a 15.2% active solution). Table 7 shows the performance of PAA at concentrations from 20 ppm to 80 ppm compared to a PFA formulation with less than 20 ppm (17 ppm).

[00122] As shown in Table 7, PFA composition provided superior disinfection properties at significantly lower actives when compared to PAA. These data are significant as a lower ppm/active level of an antimicrobial/disinfectant peroxyformic acid composition can be dosed in the wash (such as laundry).

[00123] The inventions being thus described, it will be obvious that they can be varied in many ways. These variations will not be considered as a deviation from the spirit and scope of the inventions and all such modifications are intended to be included within the scope of the following claims. The above descriptive report provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention resides in the claims.

Claims (19)

1. Method of sanitizing and/or antimicrobial disinfectant treatment and bleaching of laundry, the method characterized by the fact that it comprises: a. washing laundry with a peroxyformic acid composition at a pH range of 4 to 7 in a clothes washing machine for antimicrobial effectiveness in laundry, wherein the peroxyformic acid composition comprises peroxyformic acid, formic acid and peroxide hydrogen; after that b. add an alkalinity source to the washing machine to raise the pH range to at least above 9 in the washing machine; after that c. adding a bleach activator composition and/or catalyst composition to enhance the bleaching effectiveness of the peroxyformic acid composition on the laundry machine washable; and d. optionally, apply a laundry detergent use solution to remove dirt from the laundry at any point in the method of sanitizing and/or disinfecting and bleaching the laundry; and. draining the peroxyformic acid composition, the detergent use solution and the bleach activator composition and/or catalyst composition from the laundry, wherein (i) the peroxyformic acid composition has a weight ratio of peroxyformic acid to hydrogen peroxide of 1:1 or greater hydrogen peroxide and/or (ii) the method comprises an additional step of adding additional hydrogen peroxide to the washing machine wash at any time during the method prior to draining the acid composition peroxyformic acid, the detergent use solution and the bleach activator and/or catalyst composition of the laundry to increase the bleaching effectiveness of the peroxyformic acid composition. 2. Method according to claim 1, characterized in that the washing machine is an industrial machine or a consumer machine. 3. Method according to claim 1, characterized in that the peroxyformic acid composition is applied to the laundry to be washed in the washing machine at a pH of 5 to 7. 4. Method according to claim 1, characterized in that the peroxyformic acid composition is applied to the laundry for washing in the washing machine for 3 to 15 minutes. 5. Method according to claim 1, characterized in that the peroxyformic acid composition is generated IN SITU or at a point of use. 6. Method according to claim 1, characterized in that the peroxyformic acid composition is supplied to the washing machine at an active level of 5 ppm to 200 ppm. 7. Method according to claim 1, characterized in that the alkalinity source increases the pH range to at least above 10. 8. Method according to claim 1, characterized in that the detergent use solution and the bleach activator composition and/or catalyst composition are applied to the laundry for washing in the washing machine for 3 to 15 minutes . 9. Method according to claim 1, characterized in that the detergent use solution comprises an alkalinity agent. A method according to claim 9, characterized in that the alkalinity agent comprises at least one of alkali metal hydroxide, alkali metal silicate, alkali metal carbonate or other base component. 11. Method according to claim 1, characterized in that the detergent use solution further comprises one or more surfactants, chelants, polymers, enzymes or other functional ingredients. 12. Method according to claim 1, characterized in that the bleach activator is tetra-acetylethylene diamine, sodium nonanoyloxybenzene sulfonate (NOBS), acetyl caprolactone, N-methyl morpholinium acetonitrile or combinations thereof. 13. Method according to claim 1, characterized in that the bleaching catalyst is a transition metal catalyst. 14. Method according to claim 13, characterized in that the transition metal catalyst is a compound containing manganese. 15. Method according to claim 1, characterized in that it further comprises a step of adding additional hydrogen peroxide to the washing machine wash before or after adding the peroxyformic acid composition, before or after adding the solution of detergent use, before or after addition of the alkalinity source and/or before or after addition of the bleach activator and/or catalyst to enhance the bleaching effectiveness of the peroxyformic acid composition. 16. Method according to claim 1, characterized in that it further comprises a step of rinsing the peroxyformic acid composition, the detergent use solution and the bleach activator composition and/or the catalyst composition from the laundry to to wash. 17. Method according to claim 16, characterized in that the laundry is rinsed with water in the washing machine for at least 1 minute. 18. Method according to claim 1, characterized in that the method further comprises an adjuvant solution comprising at least one of acidifying agents, fabric softening agents, starch, anti-wrinkling agents, sizing agents, solidifying agents colorants, oil and water repellent agents, water conditioning agents, iron control agents, water threshold agents, soil release agents, soil protection agents, optical brightening agents, fragrances and mixtures thereof , and where the adjunctive use solution is applied to laundry for washing in the washing machine at a pH of 5 to 8 for 1 to 6 minutes and at any time during the method before draining the peroxyformic acid composition, the solution detergent usage and bleach activator and/or laundry catalyst composition. 19. Method according to claim 1, characterized in that the method for sanitizing and/or disinfecting and whitening the laundry follows an initial washing step for the laundry.

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